New anthraquinone dyestuffs containing a reactive triazine group



United States Patent Ofiti ce 3,070,602 Patented Dec. 25, 1962 This application is a continuation-in-part of my copending application Serial No. 802,002 filed March 26, 1959.

This invention provides water-soluble anthraquinone dyestufis of the formula (in which one of the two Xs is a hydrogen atom and the other X a chlorine atom) and advantageously radicals containing labile halogen atoms. In such radicals the labile halogen atom, that is to say, one capable of reacting with fibrous materials, may be bound to a heterocyclic radical containing two nitrogen atoms, for example, to a pyrimidine radical or to the acyl group of an acid containing at least one acid group of the constitution for example an acyl group derived from barbituric acid, cyanuric acid or an aliphatic carboxylic acid. When the acyl group is that of cyanuric acid, the dyestufl? contains at least one halogen atom bound to a 1:3:5-triazine ring, for example, a dichlorotriazine radical or a monochlorotriazine radical, such as the radical of the formula in which X represents an amino group which may be substituted or a substituted hydroxyl group. The acyl groups containing halogen and derived from aliphatic carboxylic acids advantageously contain only few carbon atoms, for example, 23 carbon atoms. As examples there may be mentioned the chloracetyl radical, the aor fi-chloropropionyl radical and above all the a-B-dichloropropionyl radical.

The invention also provides a process for the manu.

facture of the dyestuffs of the above Formula 1, wherein an anthraquinone dyestuti of the formula C0 5 soan NR-XNR1B l I n-lHZn-l Cm l hr'l in which Z, R, X, R n and m have the meanings given above, and B represents an acylatable amino group, ad.- vantageously a free amino group, is reacted with an an- '15 hydride or halide of an acid of which the acyl group is capable'of entering into chemical combination with the fibrous material, so that the acylatable amino group B is acylated.

As anhydrides or halides of acids of which the acyl group is reactive there may be mentioned, for example, the anhydrides and halides of aliphatic azfi-unsaturated carboxylic acids, for example, chloromaleic anhydride propiolic acid chloride, acrylic acid chloride and especially the halides of aliphatic carboxylic acids containing labile halogen atoms, such as chloroacetyl chloride, sulfochloracetic acid chloride, B-bromoor fi-chloro-propionic acid chloride, azfi-dichloropropionic acid chloride, and also trichloropyrimidine and preferably cyanuric chloride or a primary condensation product of cyanuric chloride which contains two chlorine atoms and, instead of the third chlorine atom, a free amino group or an inorganic radical. Such primary condensation products can be obtained by methods in themselves known from one molecular proportion of cyanuric chloride and one mo- 0 lecular proportion of a reactive organic hydroxyl-compound (for example, one molecular proportion of a phenol or alcohol), and one molecular proportion of ammonia or of an organic amine, such as methyl-amine, isopropylamine, cyclohexylamine or phenylamine, dimethyl-amine, N-ethyl-phenylamine, -y-methoxy-propylamine, phenyl-hydrazine sulfonic acids, aminoethane sulfonic acid, amino-acetic acid, ortho, metaor para-aminobenzoic acid, aminobenzene sulfonic acid, such as ortho, meta, or para-amino benzene sulfonic acid an l-aminobenzene-2:5-disulfonic acid, aminonaphthalene sulfonic acids, and also mercapto-acetic acid or the like.

The starting materials of the Formula 2 can be prepared by the usual methods, for example, by condensing 50 an aminoanthraquinone of the formula 00 -soin Halogen in which the symbol Z has the meaning given in connection with Formula 1, with an aminobenzene sulfonic acid amide or carboxylic acid amide of which the amide radical contains an acylatable amino group or an acylated amino group of which the acyl group may, be split oif by hydrolysis, if desired, after the condensation.

As aminobenzene sulfonic acid amides and carboxylic acid amides which are to be condensed with the 4-halogen-, especially 4-bromo-l-aminoanthraquinone-Z:5- or -2.6- or -2:7- or -2:8-disulfonic acid, ormore especially with the 4-bromo-1-aminoanthraquinone-Z-sulfonic acid, there may be mentioned: 1-aminobenzene-3- or -4-carboxylic acid-N-(4'-aminophenyl)-amide-3'-sulfonic acid, 1-aminobenzene-3- or -4-su1fonic acid-N-(5-amino-2- methylphenyl)-amide-4'-sulfonic acid, l-aminobenzene-3- or -4-carboxylic acid-N-(3'-aminophenyl)-amide-4'-sulfonic acid, 1-aminobenzene-3- or 4-su1fonic acid-N-(3'- aminophenyl)-amide-4'-sulfonic acid, 1-aminobenzene-3- or 4-sulfonic acid-N-(4-aminophenyl)-amide-3'-sulfonic acid, 4-methylor 4-chloro-1-aminobenzene-3-sulfonic acid-N-(3'-aminophenyl)-amide-4'-sulfonic acid, and also 1-aminobenzene-3-sulfonic acid-N-(5'- or -4"acetylaminoethyl)-amide-2-sulfonic acid, 1-aminobenzene-3- or -4-su1fonic acid-N-(3'-acetaminophenyl)-amide-4'-sulfonic acid, 1-aminobenzene-3- or -4-sulfonic acid-N-(B- acetaminoethyl)-amide, the corresponding acetylaminohexylamide and 1-aminobenzene-3- or -4-sulfonic acid-N- (3'-acetaminophenyl)-amide, of which the acetyl amino group is hydrolysed after the condensation with a 4-halogen-1-aminoanthraquinone, and others in which the benzene nucleus bearing the amino and the sulfonic acid amide or carboxylic acid amide group has as a further substituent an ethyl group.

The condensation or acylation of the dyestuffs of the Formula 2 obtainable from the above compounds is advantageously carried out in the presence of an acidbinding agent, such as sodium acetate, sodium hydroxide or sodium carbonate and bicarbonate, and under conditions such that the resulting product contains a reactive substituent, more especially a reactive halogen atom. Thus, the acylation may be carried out, for example, in an organic solvent or at a relatively low temperature in an aqueous medium. When cyanuric chloride is used as acylating agent the dyestuff formed by the primary condensation and having the formula in which Z, R, X, R m and n have the meanings given in connection with Formula 1, and Y represents a 2:4- dichloro-1z3z5-triazine ring bound in the 6-position through an amino bridge to R is reacted with ammonia, an alcohol or a phenol or more especially with an organic monamine to form a secondary condensation product, the reaction being advantageously carried out at a somewhat raised temperature, for example, within the range of 30 C. to 90 C., and advantageously 40 C. to 60 C., whereby the condensation proceeds more rapidly and completely than at lower temperatures, and it is surprising that the third chlorine atom of the cynauric chloride is not attacked.

The dyestuffs of the Formula 1 are new. They are valuable dyestufis for dyeing or printing a very wide variety of materials, especially nitrogenous fibers such as wool, superpolyamides, leather, silk, and also polyhydroxylated materials of fibrous structure, such as cellulosic materials including synthetic fibers, for example of regenerated cellulose, and natural materials, for example, linen, cellulose or above all cotton. They are suitable for dyeing polyhydroxylated fibrous materials by the so-called direct dyeing methods and also by the paddyeing method, especially from an alkaline aqueous solution, which may contain a high concentration of salt, for example, by the process in which the dyestuif is fixed on the material by means of an acid-binding agent at a raised temperature. The dyeing of nitrogenous fibers, such as wool, is advantageously carried out from an acid to neutral bath, if desired, in the presence of a compound containing at least one basic nitrogen atom, to which is bound at least one radical containing a polyglycol ether chain, the molecule containing at least four (advantageously -CH -CH -O- groups) and at least four carbon atoms not forming part of such groups, for example, in the presence of a nitrogen compound of the formula in which R represents an, advantageously unbranched, aliphatic hydrocarbon radical containing at least 12, and preferably 16-20, carbon atoms, and p and q each represent a whole number and the sum of p q is at least 4 and preferably 6-16.

The dyeings and prints produced with the dyestuffs of the Formula 1 are in general distinguished by the brilliance and the purity of their reddish blue tints, by their good fastness to chlorine and light and above all by their excellent fastness to washing.

The following examples illustrate the invention, the parts being by weight:

Example 1 38.2 parts of 1-amino-4-bromanthraquinone-Z-sulfonic acid and 44.0 parts of 4-aminotoluene-2-sulfonic acid-N- (3-acetyl-aminophenyl)-amide-4-sulfonic acid are pasted in 400 parts of water and mixed with 60 parts of sodium bicarbonate. 1 part of cuprous chloride is added and the mixture is heated to and stirred at to C. until brornamino-anthraquinone-sulfonic acid can no longer be detected. The blue dyestuff of the formula (III) NHg o NHQ-CH: NHCOOH! is separated by acidification and salting out, filtered off and, if desired, washed with sodium chloride solution.

To hydrolyse the acetyl group and liberate the amino group, the resulting dyestutf paste is stirred in 200 parts of water, heated to 80 C. and refluxed for several hours with 400 parts of a sulfuric acid solution of tit-naphthalenesulfonic acid containing 30% by weight of a-naphthalenesulfonic acid. On cooling, the hydrolyzed dyestutf precipitates in crystalline form.

parts of ice are added to a solution of 19 parts of cyanuric chloride in 80 parts of acetone. The resulting suspension of cyanuric chloride is run into a neutralized solution, cooled to +2 C., of 65.8 parts of the dyestuff of the formula SOsH NH C NH:

BOaNH SOIH 5 6 reaction mixture is maintained constant at pH=6 to 7. d After stirring for about 2 hours the condensation is com- H: plate. A neutralized solution of 17.3 parts of l-aminobenzene-3-sulfonic acid in 500 parts of water is added, COOH: and the reaction mixture is slowly raised to a temperature 5 SOPNH 41113 of 30 to 50 C., and the liberated acid is again continually neutralized with a total of 50 parts by volume SOaH of 2 N-sodium hydroxide solution. On completion of the reaction the resulting dyestuff is salted out with socan likewise be prepared in analogous manner by usdium hloride, filte ed off a d dri d; it .f a bl 10 ing instead of para-nitrotoluene-ortho-sulfonyl chloride powder which dissolves in water with blue coloration corresponding Proportions f -nitm-z-chloflobenzeile-1- and in concentrated sulfuric acid with green-blue colocrasulfonyl Chloride 0f meta'nitrobellzenesulfonyl chtion and dyes cotton and regenerated cellulose by the Iide- Examplez process described in Example 6 full, reddish blue tints of When in Example 1, paragraphs 1 to 3, instead of 4- amino-l-methylbenzene 2 sulfonic' acid-N-(3-acetylaminophenyl)-amide-4'-sulfonic acid, 40 parts of'4-amin0- 1-methylbenzene 2 sulfonic acid-N-(B'aminophenyD amide-4'-su1fonic acid are condensed with 38.2 parts of 1- amino-4-bromanthraquinone-Z-sulfonic acid'at 60 to 70 C. instead of at 8090 C., and the reaction mixture is further worked up, a dyestuff is obtained which has identical properties.

good fastness to washing and light.

Prior to the condensation with 1-aminobenzene-3 sulfonic acid, the corresponding dichloro-dyestulf can be isolated in powder form by addition of salt, filtration and drying; it dyes wool and cotton blue tints.

When wool is dyed with this dyestutf from a weakly acetic acid bath, valuable blue tints of good fastness properties are likewise obtained.

The 4-amino-l-methylbenzene-2-sulfonic acid-N-(3'- Example3 (I) NH:

SOtH it so H H N/ \III I a o NH-O NH-! C-NH-O SOINH SOaH HOsS acetyl-aminophenyl)-amide-4'-sulfonic acid used in this 100 parts of ice are added to a solution of 19 parts of example can be prepared, for example, as follows: cyanuric chloride in 80 parts of acetone. The resulting 23.5 parts of para-nitrotoluene-ortho-sulfonyl chloride suspension of cyanuric chloride is mixed with a solution,

and 19.0 parts of 2:4-diaminobenzenesulfonic acid are cooled to 0 C., of 32.7 parts of the disodium salt of lpasted in 500 parts of water and at a slightly raised aminobenzene-Z:S-disulfonic acid in 330 parts of water.

temperature the reaction mixture is kept weakly alkaline In the course of 2 hours 55 parts by volume of 2N- by addition of 10 parts of sodium hydroxide solution of sodium carbonate solution are added dropwise, while 30% strength. On completion of the condensation the maintaining the temperature at 2 t0 4 C. by external sulfonamide formed is quantitatively precipitated by cooling. A clear solution is obtained of the condensaacidification with hydrochloric acid, filtered oil and, if tion product from equimolecular proportions of cyanuric desired, washed. chloride and 1-aminobenzene-2:S-disulfonic acid which,

The crude crystalline mass is then dissolved in 100 if desired, can then be purified by being filtered. parts of water by adding 10 parts of sodium hydroxide The resulting solution is added to an aqueous neutral solution of 30% strength. parts of acetanhydride are solution, heated at 40 C., of 64.3 parts of the dyestutf added, whereupon acetylation sets in spontaneously with 50 of the formula evolution of heat, and the acetyl derivative precipitates 0 NH, in magnificent crystals.

The reduction of the nitro group is carried out in the S0311 conventional manner by Bchamps method with iron and hydrochloric acid. When the reduction mixture is alkalinised, purified by filtration, acidified and treated H I with sodium chloride, the 4-amino-l-methylbenzene-Z- 0 NH 1 NH; sulfonic acid-N-(3'-acetylarninophenyl)-amide-4'-sulfonic acid is obtained in crystalline form. s0=NH When the 2:4-diaminobenzenesulfonic acid is replaced by 23 parts of 4-acetylarnino-2-aminobenzenesulfonic t acid, preceeding otherwise in identical manner, 4-amino- 111 1500 Parts Water, and the P Value Of the reactloll 1 methyl benzene 2 sulfonic acid-N-(5'-acylaminomlxturq mamtamed constant at P to 7 the gradp i z lf i acid is obtained ual addition of 50 parts by volume of 2N-sod1um hydrox- The compounds of the formula ide solution. On completion of the condensation the dyestuff is salted out with sodium chloride, filtered ofi and dried in a vacuum cabinet at to 80 C. It forms a blue powder which dissolves in water with blue colora- NHI tion and dyes cotton by the method described in Exam- 70 ple 6 reddish blue tints which are fast to washing and light. By the method described above furthed dyestuffs which -SO3-NH NHCOCH; dye reddish,blue tints are obtained by condensing cyanu'ric chloride or cyanuric bromide with the anthrasopg quinone dyestuffs shown in column I of the following 1 table and with the compounds incolumn II Ammonia.

2-aminopr0pano1.

Mercaptoacetic acid.

'y-Methoxyptopylamme.

Phenol.

1-aminobenzene-2z5-disulfonic acid.

I II

C O s 01H NH S OaNH -NH; 1-amin0benzcne4 sulionic acid.

-CH: S 03H O 0 1e. -s 0m NH S O zNH -NH, 1-hydroxybenzene-4-sultonic acid.

CH; S 0 311 Example 4 S-aminobenzenesulfonic acid N-(fi acetamino-ethyl)- amide is prepared by acylating monoacetyl-ethylenediamine with 3-nitrobenzenesulfonyl chloride and reducing the nitro group in the resulting diacyl derivative to an NH -group.

30.8 parts of this product are condensed with 38.2 parts of l-amin0-4-bromanthraquinone-Z-sulfonic acid and parts of sodium bicarbonate in the presence of cuprous chloride in an aqueous medium, and after filtration the isolated dyestufi paste is refluxed at the boil for a prolonged period with 250 parts of a sulfuric acid solution of about 15% strength of a-naphthalenesulfonic acid for the purpose of the hydrolysis of the acetylamino group. Filtration of the reaction mixture yields the dyestufi of the formula 00 soar or its sulfate respectively.

51.6 parts of this dyestuff in 1500 parts of water are neutralized with sodium hydroxide. The neutral solution is treated with an aqueous solution (prepared from 19 parts of cyanuric chloride and 32.7 parts of the disodium salt of 1-aminobenzene-2:S-disulfonic acid) of the primary condensation product which, in the form of the free acid, corresponds to the formula The pH value of the reaction mixture is kept constant at 6 to 7 by gradually adding a 2 N-aqueous solution of sodium hydroxide. On completion of the condensation the dyestufi is salted out with sodium chloride, filtered off and dried in a vacuum cabinet at to C. It forms a blue powder which dissolves in water with blue coloration and dyes cotton by the method described in Example 6 reddish blue tints which are fast to washing and light.

Further dyestutfs which produce similar tints are obtained by this method when the anthraquinone dyestuffs shown in column I of the following table are condensed in an analogous manner with the compounds in column II.

1 part of the dyestutf obtained as described in Example 3 is dissolved in 100 parts of Water. A fabric of regenerated cellulose staple fiber is impregnated with the resulting solution until the fabric shows an increase in weight of 75% and then dried. The fabric is then impregnated with a solution of 20 C. containing per liter grams of sodium hydroxide and 300 grams of sodium chloride, squeezed to a weight increase of 75 the dyeing is steamed for 60 seconds at 100 to 101 C., rinsed, treated in a sodium bicarbonate solution of 0.5% strength, rinsed, soaped for minutes in a boiling solution of a non-ionic detergent of 0.3% strength, rinsed and dried. A reddish blue dyeing results.

Example 6 A dyebath is prepared from 4000 parts of water, 5 parts of acetic acid of strength, 10 parts of crystalline sodium sulfate, 1 part of the addition product described below of octadecenylamine and ethylene oxide and 2 parts of the dyestuff of the formula SOaNH HOaS I II

N 3- /CO SO:H Cl0 c-o t, i. \00 \C/ SOaH NH SO2NH 11 HzCHzNH:

N112 N 4.... /C0 -SO3H (ll-0 co SOBH l t oo o NH S02-NH (:1

OHzCHg-NHa N /CO -SO3H C10% o-o t \00 SOaH NH S0zNH n diatom-NH,

NH: N 6---. /c0 SO;H 01-43 \GNH SO=H i. t \00 HOSS NHO-s0lNH(oH2 z-NH2 (J1 Example 5 At 60 C., parts of woolen piece goods are immersed in this dyebath which is then raised to the boil within half an hour, and dyeing at the boil is performed for 1 hour. The wool is then withdrawn from the dyebath-if desired, after addition of 0.8 part of an aqueous ammonia solution of 25% strengthimmediately rinsed in Water and dried. A level reddish blue dyeing is obtained which has good fastness to light and wetting.

The ethylene oxide addition product is prepared in the following manner:

100 parts of commercial octadecenylamine are mixed with 1 part of finely disintegrated sodium, the whole is heated to 140 C. and ethylene oxide is introduced at to C. When the ethylene oxide is being consumed rapidly, the reaction temperature is lowered to 120125 C., and the introduction of ethylene oxide is continued until 113 parts thereof have been absorbed. The resulting reaction product gives an almost clear solution in water.

Example 7 1 part of the monochloro-triazine dyestuif obtained 'as SOsH described in Example 1 is dissolved in parts of water and stirred into 1175 parts of a viscose Xanthate solution of 8.5% strength, corresponding to a content of 100 parts of cit-cellulose. The mass is stirred for A hour and then stored for hours at room temperature.

The viscose mass is then spun through spinnerets, in the manner conventionally employed for the manufacture of viscose rayon yarn, and coagulated at 45 C. in a precipitation bath containing per liter 120 grams of sulfuric acid of 96% strength, 270 grams of sodium sulfate and 10 grams of zinc sulfate.

The resulting filaments are stretched by 25% and collected in a spinning can rotating at 6000 revolutions per minute.

The cake obtained in this manner is after-treated in a closed apparatus with circulating liquor; it is first rinsed for 10 minutes with water heated at 60 to 70 C., then desulfurized for 20 minutes at 70 C. with a solution containing per liter 5 grams of sodium sulfite, then again rinsed, and finally brightened for 10 minutes at 50 C. with a solution of 50 grams of sodium oleate per liter.

The cake is then freed from its water content and dried. A blue dyeing is obtained which is fast to washing.

00 son;

wherein X represents a member selected from the group consisting of the CO and the SO;- bridge;

Y represents a member selected from the group consisting of chlorine and bromine;

A represents a member selected from the group consisting of chlorine, bromine, and the amino, lower alkyl amino, lower alkoxy-lower alkylarnino, lower hydroxyalkylamino, cyclohexylamino, monocyclic arylamino, dicyclic arylamino, lower alkoxy, monocyclic aryloxy, dicyclic aryloxy, sulfophenyl-hydrazinyl, sulfo-ethaneamino and mercapto-acetic acid radicals;

Z represents a member selected from the group consisting of hydrogen and the sulfonic acid group;

R represents a member selected from the group consisting of hydrogen, chlorine, methyl and ethyl; and

R represents a member selected from the group consisting of the phenylene and lower alkylene radicals having maximally 6 carbon atoms.

2. The water-soluble anthraquinone dyestufi of the formula 3. The water-soluble anthraquinone dyestufi of the formula 4. The anthraquinone dyestuif of the formula 00 0 SOaH 3 HO S so H C0/ a f/ 3 NH SOzNH NH f7-NH sonar What is claimed is: 1. A water-soluble anthraquinone dyestufi of the 5. The anthraquinone dyestuff of the formula formula NH; NH:

00 /C0\ sosn -soner 01 N 6 H038 CO X-NH-lh-NH-C lC-Y CO III N z NH fr NH SOzNH NHC fJ-oo1r,

6. The anthraquinone dyestufl? of the formula /CO 803B 21 I IH S O2NHOH2CH|NH- (II-NH I SOzH References Cited in the file of this patent OTHER REFERENCES UNITED STATES PATENTS 15 Schlaeppi: American Dyestufi Reporter, v01. 47, pp. 377-383, June 2, 1958.

$32, 3 ,11 111112311 533 i332 Vickerstaif: Melliand Textilberichte, v01. 39, pages 905- 2,195,067 Weinand et a1 Mar. 26, 1940 August 1958- 2333137 Zerweck et a1 2, 1943 Hess et al.: Nature, vol. 18.3, pages 260-261, Jan. 24, 2430771 Kern 1947 Smo1in et a1 s Triazines and Derivatives Inter 2730534 Hoefie et 1956 science Publishers Inc., New York, 1959, pages 52, 53,

FOREIGN PATENTS 2, 1 1 and 217 91,206 Norway Jan. 18, 1958 25 531,250 Belgium Feb. 19, 1955 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 8,070,602 December 135, 1962 Arthur Buehler It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 62, for "may, be" read may be column 3, lines 34 to 42, the formula should appear as shown below instead of as in the patent:

N R x N R1 Y column 9, under the heading "I", the upper left hand portion of formula No. 14 should appear as shown below instead 0L as in the patent:

column 13, under the heading "I", extreme righthand portion of formula N0. 6, for "(CH )tNH read? (CH NH -a Signed and sealed this 12th day of November 1963w (SEAL) Attest:

EDWIN L, REYNoLss Acting Commissioner of Patents ERNEST W. SWIDE-R Attesting Officer 

1. A WATER-SOLUBLE ANTHRAQUINONE DYESTUFF OF THE FORMULA 